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An important goal of the modern soft matter science is to discover new self-assembly modalities to precisely control the placement of small particles in space. Spatial inhomogeneity of liquid crystals offers the capability to organize colloids in certain regions such as the cores of the topological defects. Here we report two self-assembly modes of nanoparticles in linear defects-disclinations in a lyotropic colloidal cholesteric liquid crystal: a continuous helicoidal thread and a periodic array of discrete beads. The beads form one-dimensional arrays with a periodicity that matches half a pitch of the cholesteric phase. The periodic assembly is governed by the anisotropic surface tension and elasticity at the interface of beads with the liquid crystal. This mode of self-assembly of nanoparticles in disclinations expands our ability to use topological defects in liquid crystals as templates for the organization of nanocolloids. [ABSTRACT FROM AUTHOR]

Cellulose nanocrystals (CNCs) form cholesteric films that exhibit birefringence, iridescence, and circular dichroism; however, these films are brittle and prone to cracking. Here we report composite cholesteric films formed from CNCs and soft reactive latex nanoparticles (NPs) (the latter underwent in situ cross-linking during film formation). Composite films exhibited a self-stratified morphology, with lateral cholesteric CNC-rich layers and isotropic latex NP-rich layers. The films retained their photonic properties and exhibited significantly enhanced mechanical properties. In comparison with latex-free CNC films, composite films had an ~60% higher toughness but did not compromise their tensile strength. The combination of photonic performance and improved mechanical properties of the composite nanocellulose films expands the range of applications of these materials for the fabrication of optical devices. [ABSTRACT FROM AUTHOR]

We build on the concept of hot intrusion embossing to develop a one-step fabrication method for thermoplastic microfluidic channels containing integrated three-dimensional features. This was accomplished with simple, rapid-to-fabricate imprint templates containing microcavities that locally control the intrusion of heated thermoplastic based on their cross-sectional geometries. The use of circular, rectangular and triangular cavity geometries was demonstrated for the purposes of forming posts, multi-focal length microlense arrays, walls, steps, tapered features and three-dimensional serpentine microchannels. Process variables, such as temperature and pressure, controlled feature dimensions without affecting the overall microchannel geometry. The approach was demonstrated for polycarbonate, cycloolefin copolymer and polystyrene, but in principle is applicable to any thermoplastic. The approach is a step forward towards rapid fabrication of complex, robust, microfluidic platforms with integrated multi-functional elements. [ABSTRACT FROM AUTHOR]

We report composite stimulus-responsive cholesteric catalytically active microgels derived from filamentous supramolecular building blocks: cellulose nanocrystals (CNCs). The variation in the microgel dimensions and pitch in response to the change in ambient conditions was governed by the polymer component. The cholesteric morphology of the microgels resulted from the self-organization of CNCs in spherical confinement. The microgels exhibited excellent structural integrity and functioned as microreactors in catalytic hydrolysis reactions and in the synthesis of metal nanoparticles. Because of these collective properties, the reported microgels show much promise for application in the design of functional responsive materials. [ABSTRACT FROM AUTHOR]

We report composite stimulus-responsive cholesteric catalytically active microgels derived from filamentous supramolecular building blocks: cellulose nanocrystals (CNCs). The variation in the microgel dimensions and pitch in response to the change in ambient conditions was governed by the polymer component. The cholesteric morphology of the microgels resulted from the self-organization of CNCs in spherical confinement. The microgels exhibited excellent structural integrity and functioned as microreactors in catalytic hydrolysis reactions and in the synthesis of metal nanoparticles. Because of these collective properties, the reported microgels show much promise for application in the design of functional responsive materials. [ABSTRACT FROM AUTHOR]

Natural extracellular matrices often have a filamentous nature, however, only a limited number of artificial extracellular matrices have been designed from nanofibrillar building blocks. Here we report the preparation of temperature-responsive nanofibrillar hydrogels from rod-shaped cellulose nanocrystals (CNCs) functionalized with a copolymer of N-isopropylacrylamide and N,N′-dimethylaminoethyl methacrylate. The composition of the copolymer was tuned to achieve gelation of the suspension of copolymer-functionalized CNCs at 37 °C in cell culture medium and gel dissociation upon cooling it to room temperature. The mechanical properties and the structure of the hydrogel were controlled by changing copolymer composition and the CNC-to-copolymer mass ratio. The thermoreversible gels were used for the encapsulation and culture of fibroblasts and T cells and showed low cytotoxicity. Following cell culture, the cells were released from the gel by reducing the temperature, thus, enabling further cell characterization. These results pave the way for the generation of injectable temperature-responsive nanofibrillar hydrogels. The release of cells following their culture in the hydrogels would enable enhanced cell characterization and potential transfer in a different cell culture medium. [ABSTRACT FROM AUTHOR]

Liquid–liquid extraction is an important separation and purification method; however, it faces a challenge in reducing the energy consumption and the environmental impact of solvent (extractant) recovery. The reversible chemical reactions of switchable solvents (nitrogenous bases) with carbon dioxide (CO2) can be implemented in reactive liquid–liquid extraction to significantly reduce the cost and energy requirements of solvent recovery. The development of new effective switchable solvents reacting with CO2 and the optimization of extraction conditions rely on the ability to evaluate and screen the performance of switchable solvents in extraction processes. We report a microfluidic strategy for time- and labour-efficient studies of CO2-mediated solvent extraction. The platform utilizes a liquid segment containing an aqueous extractant droplet and a droplet of a solution of a switchable solvent in a non-polar liquid, with gaseous CO2 supplied to the segment from both sides. Following the reaction of the switchable solvent with CO2, the solvent becomes hydrophilic and transfers from the non-polar solvent to the aqueous droplet. By monitoring the time-dependent variation in droplet volumes, we determined the efficiency and extraction time for the CO2-mediated extraction of different nitrogenous bases in a broad experimental parameter space. The platform enables a significant reduction in the amount of switchable solvents used in these studies, provides accurate temporal characterization of the liquid–liquid extraction process, and offers the capability of high-throughput screening of switchable solvents. [ABSTRACT FROM AUTHOR]

Fabrication of anisotropic hydrogels exhibiting direction-dependent structure and properties has attracted great interest in biomimicking, tissue engineering, and bioseparation. Herein, we report a freeze-casting-based fabrication of structurally and mechanically anisotropic aerogels and hydrogels composed of hydrazone cross-linked poly(oligoethylene glycol methacrylate) (POEGMA) and cellulose nanocrystals (CNCs). We show that, by controlling the composition of the CNC/POEGMA dispersion and the freeze-casting temperature, aerogels with fibrillar, columnar, or lamellar morphologies can be produced. Small-angle X-ray scattering experiments show that the anisotropy of the structure originates from the alignment of the mesostructures, rather than the CNC building blocks. The composite hydrogels show high structural and mechanical integrity and a strong variation in Young's moduli in orthogonal directions. The controllable morphology and hydrogel anisotropy, coupled with hydrazone cross-linking and biocompatibility of CNCs and POEGMA, provide a versatile platform for the preparation of anisotropic hydrogels. [ABSTRACT FROM AUTHOR]

Fundamental studies and practical use of metal nanoparticles (NPs) frequently depend on the ability to reproducibly synthesize large quantities of shape-specific NPs. For this reason, facile synthetic procedures are desired that will lead to large quantities of uniformly sized metal NPs exhibiting specific shapes. Here, we report a general approach to the large-scale synthesis of noble metal nanocrystals having well-defined shapes and a narrow size distribution. This method utilizes seed-mediated NP growth in aqueous suspensions of cationic surfactants and metal salts. It leads to a ~60-fold increase in NP volumetric production capacity, compared to the most widely used solution-based synthetic methods. In addition, it uses up to 100 times less cationic surfactant than conventional solution-based methods. The applicability of the method is demonstrated in the synthesis of Pd nanocubes, rhombic dodecahedra, and polyhedrons with low index facets; branched Pd nanocrystals; alloy Pt/Pd nanocubes; Ag nanocubes. The advantages and limitations of the approach are discussed, including accessible shapes, growth kinetics, and the capability to scale up the synthetic procedure. [ABSTRACT FROM AUTHOR]

Microscale technologies offer the capability to generate in vitro artificial cellular microenvironments that recapitulate the spatial, biochemical, and biophysical characteristics of the native extracellular matrices and enable systematic, quantitative, and high-throughput studies of cell fate in their respective environments. We developed a microfluidic platform for the generation of two-dimensional arrays of micrometer-size cell-laden hydrogel modules (HMs) for cell encapsulation and culture. Fibroblast cells (NIH 3T3) and non-adherent T cells (EL4) encapsulated in HMs showed high viability and proliferation. The platform was used for real-time studies of the effect of spatial constraints and structural and mechanical properties of HMs on cell growth, both on the level of individual cells. Due to the large number of cellladen HMs and stochastic cell distribution, cell studies were conducted in a time- and labor efficient manner. The platform has a broad range of applications in the exploration of the role of chemical and biophysical cues on individual cells, studies of in vitro cell migration, and the examination of cell-extracellular matrix and cell-cell interactions. [ABSTRACT FROM AUTHOR]

The article informs that photothermally modulated volume transitions in polymer hydrogels have promising applications in materials science and in drug delivery. To induce such transitions, photosensitive moieties are embedded in a thermally reversible polymer matrix and irradiated at their resonance wave-lengths. Conversion of the light energy to heat through non-radiative relaxation causes hydrogel heating and, for polymers with a lower critical solution temperature, results in their volume phase transition. In conclusion, the authors have demonstrated a new excellent example of materials with structural hierarchy, polymer microgel particles doped with gold nanorods. They used the variation of the longitudinal surface plasmon of the nanorods with their aspect ratio to tune absorption of the hybrid microgels into the near-IR spectral range.

Nanoparticle (NP) dispersions are extensively used for the producing nanocomposite materials. Optimization of formulations of NP dispersions is a time- and labor-consuming process that can benefit from high-throughput preparation of composite materials, followed by studies of their structure-property relationships. This paper describes a microfluidic platform for producing photopolymerized films from NP-monomer dispersions. The platform enables rapid and reproducible preparation of films with varying compositions by tuning the flow rates of the monomer and NP-monomer mixtures, along with suppressed evaporation of volatile monomers, no need of an inert atmosphere, and the reduced exposure to potentially harmful monomers and NPs. This work paves the way for efficient studies of composition-dependent properties of nanocomposite materials. [ABSTRACT FROM AUTHOR]

Reports on a strategy for the production of hybrid periodically structured nanocomposites containing semiconductor of metal nanoparticles (NP). In situ synthesis of NP on the surface of polymer microspheres by employing ion exchange of counterions in the electrical double layer of latex beads; Use of three-layer hybrid core-shell particles as the structural units of the nanocomposite material.

The entropically driven coassembly of nanorods (cellulose nanocrystals, CNCs) and nanospheres (dye-labeled spherical latex nanoparticles, NPs) was studied in aqueous suspensions and in solid films. In mixed CNC-latex suspensions, phase separation into an isotropic latex-NP-rich and a chiral nematic CNC-rich phase took place; the latter contained a significant amount of latex NPs. Drying the mixed suspension resulted in CNC-latex films with planar disordered layers of latex NPs, which alternated with chiral nematic CNC-rich regions. In addition, fluorescent latex NPs were embedded in the chiral nematic domains. The stratified morphology of the films, together with a random distribution of latex NPs in the anisotropic phase, led to the films having close-to-uniform fluorescence, birefringence, and circular dichroism properties. [ABSTRACT FROM AUTHOR]

The entropically driven coassembly of nanorods (cellulose nanocrystals, CNCs) and nanospheres (dye-labeled spherical latex nanoparticles, NPs) was studied in aqueous suspensions and in solid films. In mixed CNC-latex suspensions, phase separation into an isotropic latex-NP-rich and a chiral nematic CNC-rich phase took place; the latter contained a significant amount of latex NPs. Drying the mixed suspension resulted in CNC-latex films with planar disordered layers of latex NPs, which alternated with chiral nematic CNC-rich regions. In addition, fluorescent latex NPs were embedded in the chiral nematic domains. The stratified morphology of the films, together with a random distribution of latex NPs in the anisotropic phase, led to the films having close-to-uniform fluorescence, birefringence, and circular dichroism properties. [ABSTRACT FROM AUTHOR]

Adsorption of polymers from solutions moving past solid or liquid surfaces controls a broad range of phenomena in science, technology, and medicine. In the present work, a microfluidic methodology was developed to study polymer adsorption in flow under well-defined conditions by integrating an attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectrometer with a microfluidic device. Polymer adsorption in flow using exemplary polyelectrolytes such as polystyrene sulfonate and polyacrylic acid was studied under varying flow rates, polymer concentrations, pH values, and ionic strengths of the solution. Furthermore, the microfluidic platform was utilized to study layer-by-layer adsorption of alternating anionic and cationic polyelectrolytes such as polyacrylic acid and polyallylamine hydrochloride. The proposed methodology paves the way for studies of in-flow adsorption of biologically relevant molecules, which would mimic processes occurring in the cardiovascular microcirculation system. [ABSTRACT FROM AUTHOR]

Nanofibrillar supramolecular hydrogels are hierarchical structures formed by physical association of high-aspect-ratio nanoscale building blocks, each containing many molecules held together via supramolecular interactions. Nanofibrils have diameters in the range of tens to hundreds of nanometers, and their lengths can exceed micrometers. The driving forces involved in the formation of nanofibrillar structures include hydrogen bonding, hydrophobic forces, forces of electrostatic origin, and guest–host interactions. Nanofibrillar hydrogels are formed by biopolymers such as proteins and polysaccharides, and by synthetic supramolecular units such as cylindrical micelles of block copolymers and peptide amphiphiles. In the present review, we discuss the hierarchical assembly of nanofibrillar hydrogels, give examples of hydrogels formed by the most important groups of polymers, discuss structure–property relationships of these nanofibrillar hydrogels, and review their current and potential applications in the fields of bioengineering, cell biology, medicine, and cosmetics. [ABSTRACT FROM AUTHOR]

Solution-based linearself-assembly of metal nanoparticles offersa powerful strategy for creating plasmonic polymers, which, so far,have been formed from spherical nanoparticles and cylindrical nanorods.Here we report linear solution-based self-assembly of metal nanocubes(NCs), examine the structural characteristics of the NC chains, anddemonstrate their advanced optical characteristics. In comparisonwith chains of nanospheres with similar dimensions, composition, andsurface chemistry, predominant face-to-face assembly of large NCscoated with short polymer ligands led to a larger volume of hot spotsin the chains, a nearly uniform E-field enhancement in the gaps betweencolinear NCs, and a new coupling mode for NC chains due to the formationof a Fabry–Perot resonatorstructure formed by face-to-face bonded NCs. The NC chains exhibitedstronger surface-enhanced Raman scattering in comparison with linearassemblies of nanospheres. The experimental results were in agreementwith finite difference time domain simulations. [ABSTRACT FROM AUTHOR]

The preparation of composite biopolymer hydrogels offers the capability to produce biocompatible and biodegradable materials with cooperative properties. In this paper, two natural polymers, namely, chitosan and agarose were employed to prepare composite hydrogels with dual pH and temperature properties. The elastic modulus of the composite hydrogels increased with agarose concentration reaching the value of 1 kPa for the chitosan/agarose gel with a 2% (w/v) concentration of agarose. In addition, composite gels exhibited a higher stability in acidic aqueous solutions, in comparison with agarose gels. The drug release properties of the composite hydrogels were tested by loading a model anticancer drug, 5-Fluorouracil, in the hydrogel interior. At pH = 7.4, the cumulative release of 5-FU was ~50% within 96 h and decreased to ~33% at pH = 5.2, which was attributed to the different solubility of 5-FU as a function of pH. The preparation of composite microgels with controllable dimensions in the range from 42 to 18 µm and with narrow size distribution (polidispersity not exceeding 1.5%) was achieved by the microfluidic emulsification of an aqueous mixture of chitosan and agarose and subsequent gelation of the precursor droplets by cooling. [ABSTRACT FROM AUTHOR]

Increase in the ionic strength of water that is mediated by the reaction of carbon dioxide (C 0 2) with nitrogenous bases is a promising approach toward phase separation in mixtures of water with organic solvents and potentially water purification. Conventional macroscale studies of this complicated process are challenging, due to its occurrence via several consecutive and concurrent steps, mass transfer limitation, and lack of control over gas—liquid interfaces. We report a new microfluidic strategy for fundamental studies of liquid—liquid phase separation mediated by CO2 as well as screening of the efficiency of nitrogenous agents. A single set of microfluidic experiments provided qualitative and quantitative information on the provided qualitative and quantitative information on the kinetics and completeness of water—tetrahydrofuran phase separation, the minimum amount of CO2 required to complete phase separation, the total CO2 uptake, and the rate of CO2 consumption by the liquid mixture. The efficiency of tertiary diamines with different lengths of alkyl chain was examined in a time- and labor-efficient manner and characterized with the proposed efficiency parameter. A wealth of information obtained using the MF methodology can facilitate the development of new additives for switchable solvents in green chemistry applications. [ABSTRACT FROM AUTHOR]

Review: recent advances in the field of self-assembled plasmonic nanostructures, their optical properties and applications; 186 refs. [ABSTRACT FROM AUTHOR]

To develop an understanding of thenature of complex, spatiotemporalinteractions between cells and the extracellular matrix (ECM), artificialECMs formed from hydrogels with a particular spectrum of propertiesare being developed at a rapid pace. We report the microfluidic generationof small, monodisperse composite agarose–gelatin hydrogel modules(microgel particles) that can be used for cell encapsulation and canserve as instructive cellular microenvironments. The agarose componentof the microgels gelled under reduced temperature, while gelatin modifiedwith phenolic hydroxyl groups underwent peroxidase-catalyzed gelation.Microgel composition, structure, morphology, and rigidity were tunedin a high-throughput manner. The results of this work are importantfor the generation of libraries of cell-laden polymer microgels forsingle-cell analysis, tissue engineering, and fundamental studiesof the role of local microenvironments in cell fate. [ABSTRACT FROM AUTHOR]

We introduce oscillatory segmented flow as a compact microfluidic format that accommodates slow chemical reactions for the solution-phase processing of colloidal nanomaterials. The strategy allows the reaction progress to be monitored at a dynamic range of up to 80 decibels (i.e., residence times of up to one day, equivalent to 720–14 400 times the mixing time) from only one sensing location. A train of alternating gas bubbles and liquid reaction compartments (segmented flow) was initially formed, stopped and then subjected to a consistent back-and-forth motion. The oscillatory segmented flow was obtained by periodically manipulating the pressures at the device inlet and outlet via square wave signals generated by non-wetted solenoid valves. The readily implementable format significantly reduced the device footprint as compared with continuous segmented flow. We investigated mixing enhancement for varying liquid segment lengths, oscillation amplitudes and oscillation frequencies. The etching of gold nanorods served as a case study to illustrate the utility of the approach for dynamic characterization and precise control of colloidal nanomaterial size and shape for 5 h. Oscillatory segmented flows will be beneficial for a broad range of lab-on-a-chip applications that require long processing times. [ABSTRACT FROM AUTHOR]

Chiral plasmonic films have been prepared by incorporating gold nanorods (NRs) in a macroscopic cholesteric film formed by self-assembled cellulose nanocrystals (CNCs). Composite NR-CNC films revealed strong plasmonic chiroptical activity, dependent on the photonic properties of the CNC host and plasmonic properties of the NRs. The plasmonic chiroptical properties of the composite films were tuned by changing the conditions of film preparation. The strategy presented herein paves the way for the scalable and cost-efficient preparation of plasmonic chiral materials. [ABSTRACT FROM AUTHOR]

Frustrated Lewis pairs (FLPs) comprising sterically hindered Lewis acids and bases offer the capability to reversibly capture CO2 under mild reaction conditions. The determination of equilibrium constants and thermodynamic properties of these reactions should enable assessment of the efficiency of a particular FLP system for CO2sequestration and provide insights for design of new, efficient formulations of FLP catalysts for CO2capture. We have developed a microfluidic approach to studies of FLP–CO2reactions, which provides their thermodynamic characterization that is not accessible otherwise. The approach enables the determination of the equilibrium reaction constants at different temperatures, the enthalpy, the entropy, and the Gibbs energy of these reactions, as well as the enhancement factor. The microfluidic methodology has been validated by applying it to the well-characterized reaction of CO2with a secondary amine. The microfluidic approach can be applied for fundamental thermodynamic studies of other gas–liquid reactions. [ABSTRACT FROM AUTHOR]

The resemblance between colloidal and molecular polymerization reactions is very useful in fundamental studies of polymerization reactions, as well as in the development of new nanoscale systems with desired properties. Future applications of colloidal polymers will require nanoparticle ensembles with a high degree of complexity that can be realized by hetero-assembly of NPs with different dimensions, shapes, and compositions. A method has been developed to apply strategies from molecular copolymerization to the co-assembly of gold nanorods with different dimensions into random and block copolymer structures (plasmonic copolymers). The approach was extended to the co-assembly of random copolymers of gold and palladium nanorods. A kinetic model validated and further expanded the kinetic theories developed for molecular copolymerization reactions. [ABSTRACT FROM AUTHOR]

The resemblance between colloidal and molecular polymerization reactions is very useful in fundamental studies of polymerization reactions, as well as in the development of new nanoscale systems with desired properties. Future applications of colloidal polymers will require nanoparticle ensembles with a high degree of complexity that can be realized by hetero-assembly of NPs with different dimensions, shapes, and compositions. A method has been developed to apply strategies from molecular copolymerization to the co-assembly of gold nanorods with different dimensions into random and block copolymer structures (plasmonic copolymers). The approach was extended to the co-assembly of random copolymers of gold and palladium nanorods. A kinetic model validated and further expanded the kinetic theories developed for molecular copolymerization reactions. [ABSTRACT FROM AUTHOR]

A similarity between chemical reactions and self-assembly of nanoparticles offers a strategy that can enrich both the synthetic chemistry and the nanoscience fields. Synthetic methods should enable quantitative control of the structural characteristics of nano-particle ensembles such as their aggregation number or directionality, whereas the capability to visualize and analyze emerging nanostructures using characterization tools can provide insight into intelligent molecular design and mechanisms of chemical reactions. We explored this twofold concept for an exemplary system including the polymerization of bifunctional nanoparticles in the presence of monofunctional colloidal chain stoppers. Using reaction-specific design rules, we synthesized chain stoppers with controlled reactivity and achieved quantitative fine-tuning of the self-assembled structures. Analysis of the nanostructures provided information about polymerization kinetics, side reactions, and the distribution of all of the species in the reaction system. A quantitative model was developed to account for the reactivity, kinetics, and side reactions of nanoparticles, all governed by the design of colloidal chain stoppers. This work provided the ability to test theoretical models developed for molecular polymerization. [ABSTRACT FROM AUTHOR]

Assembly of nanoscale materials from nanoparticle (NP) building blocks relies on our understanding of multiple nanoscale forces acting between NPs. These forces may compete with each other and yield distinct stimuli-responsive self-assembled nanostructures. Here, we report structural transitions between linear chains and globular assemblies of charged, polymer-stabilized gold NPs, which are governed by the competition of repulsive electrostatic forces and attractive poor solvency/hydrophobic forces. We propose a simple quantitative model and show that these transitions can be controlled by the quality of solvent, addition of a salt, and variation of the molecular weight of the polymer ligands. [ABSTRACT FROM AUTHOR]

Microfluidics (MFs) offers a promising method for the preparation of polymer microgels with exquisite control over their dimensions, shapes and morphologies. A challenging task in this process is the generation of droplets (precursors for microgels) from highly viscous polymer solutions. Spatial separation of MF emulsification and gelation of the precursor droplets on chip can address this challenge. In the present work, we explored the application of the “direct injection” method for the preparation of microgels by adding a highly concentrated polymer solution or a gelling agent directly into the precursor droplets. In the first system, primary droplets were generated from a dilute aqueous solution of agarose, followed by the injection of the concentrated agarose solution directly in the primary droplets. The secondary droplets served as precursors for microgels. In the second system, primary droplets were generated from the low-viscous solution of methyl-β-cyclodextrin and poly(ethylene glycol) end-terminated with octadecyl hydrophobic groups. Addition of surfactant directly into the primary droplets led to the binding of methyl-β-cyclodextrin to the surfactant, thereby releasing hydrophobized poly(ethylene glycol) to form polymer microgels. Our results show that, when optimized, the direct injection method can be used for microgel preparation from highly viscous liquids and thus this method expands the range of polymers used for MF generation of microgels. [ABSTRACT FROM AUTHOR]

Recentadvances in spectrally tuned, solution-processed plasmonic nanoparticleshave provided unprecedented control over light’s propagationand absorption via engineering at the nanoscale. Simultaneous parallelprogress in colloidal quantum dot photovoltaics offers the potentialfor low-cost, large-area solar power; however, these devices sufferfrom poor quantum efficiency in the more weakly absorbed infraredportion of the sun’s spectrum. Here, we report a plasmonic–excitonicsolar cell that combines two classes of solution-processed infraredmaterials that we tune jointly. We show through experiment and theorythat a plasmonic–excitonic design using gold nanoshells withoptimized single particle scattering-to-absorption cross-section ratiosleads to a strong enhancement in near-field absorption and a resultant35% enhancement in photocurrent in the performance-limiting near-infraredspectral region. [ABSTRACT FROM AUTHOR]

Soft materials undergoing shape transformations in response to changes in ambient environment have potential applications in tissue engineering, robotics and biosensing. Generally, stimulus-responsive materials acquire two stable shapes corresponding to the "on" and "off" states of the external trigger. Here, we report a simple, yet versatile approach to induce multiple shape transformations of a planar hydrogel sheet, each triggered by a particular, well-defined external stimulus. The approach is based on the integration of small-scale multiple polymer components with distinct compositions in the composite gel sheet. In response to different stimuli, the structural components undergo differential swelling or shrinkage, which creates internal stresses within the composite hydrogel sheet and transforms its shape in a specific manner. [ABSTRACT FROM AUTHOR]

Plasmonic polymers present an interesting concept that builds on the analogy between molecular polymers and linear chains of strongly interacting metal nanoparticles. Ensemble-averaged optical properties of plasmonic polymers are strongly influenced by their structure. In the present work, we formed plasmonic polymers by using solution-based assembly of gold nanorods (NRs) end-tethered with photoactive macromolecular tethers. By using postassembly ligand photo-cross-linking, we established a method to arrest NR polymer growth after a particular self-assembly time, and in this manner, using kinetics of step-growth polymerization, we achieved control over the average degree of polymerization of plasmonic polymers. Photo-cross-linking of ligands also enabled control over the internanorod distance and resulted in the increased rigidity of NR chains. These results, along with a higher structural integrity of NR chains, can be utilized in plasmonic nanostructure engineering and facilitate advanced applications of plasmonic polymers in sensing and optoelectronics. [ABSTRACT FROM AUTHOR]

Hydrogels are networks of hydrophilic polymer chains that are swollen with water, and they are useful for a wide range of applications because they provide stable niches for immobilizing proteins and cells. We report here the marriage of hydrogels with digital microfluidic devices. Until recently, digital microfluidics, a fluid handling technique in which discrete droplets are manipulated electromechanically on the surface of an array of electrodes, has been used only for homogeneous systems involving liquid reagents. Here, we demonstrate for the first time that the cylindrical hydrogel discs can be incorporated into digital microfluidic systems and that these discs can be systematically addressed by droplets of reagents. Droplet movement is observed to be unimpeded by interaction with the gel discs, and gel discs remain stationary when droplets pass through them. Analyte transport into gel discs is observed to be identical to diffusion in cases in which droplets are incubated with gels passively, but transport is enhanced when droplets are continually actuated through the gels. The system is useful for generating integrated enzymatic microreactors and for three-dimensional cell culture. This paper demonstrates a new combination of techniques for lab-on-a-chip systems which we propose will be useful for a wide range of applications. [ABSTRACT FROM AUTHOR]

We present a new concept for studies of the kinetics of fast gas-liquid reactions. The strategy relies on the microfluidic generation of highly monodisperse gas bubbles in the liquid reaction medium and subsequent analysis of time-dependent changes in bubble dimensions. Using reactions of CO2 with secondary amines as an exemplary system, we demonstrate that the method enables rapid determination of reaction rate constant and conversion, and comparison of various binding agents. The proposed approach addresses two challenges in studies of gas-liquid reactions: a mass-transfer limitation and a poorly defined gas-liquid interface. The proposed strategy offers new possibilities in studies of the fundamental aspects of rapid multiphase reactions, and can be combined with throughput optimization of reaction conditions. [ABSTRACT FROM AUTHOR]

Further progress in the applications of self-assembled nanostructures critically depends on developing a fundamental understanding of the relation between the properties of nanoparticle ensembles and their time-dependent structural characteristics. Following dynamic generation of hot-spots in the self-assembled chains of gold nanorods, we established a direct correlation between ensemble-averaged surface-enhanced Raman scattering and extinction properties of the chains. Experimental results were supported with comprehensive finite-difference time-domain simulations. The established relationship between the structure of nanorod ensembles and their optical properties provides the basis for creating dynamic, solution-based, plasmonic platforms that can be utilized in applications ranging from sensing to nanoelectronics. [ABSTRACT FROM AUTHOR]

Abstract: Elasticity of cellular microenvironments strongly influences cell motility, phagocytosis, growth and differentiation. Currently, the relationship between the cell behaviour and matrix stiffness is being studied for cells seeded on planar substrates, however in three-dimensional (3D) microenvironments cells may experience mechanical signalling that is distinct from that on a two-dimensional matrix. We report a microfluidic approach for high-throughput generation of 3D microenvironments with different elasticity for studies of cell fate. The generation of agarose microgels with different elastic moduli was achieved by (i) introducing into a microfluidic droplet generator two streams of agarose solutions, one with a high concentration of agarose and the other one with a low concentration of agarose, at varying relative volumetric flow rate ratios of the two streams, and (ii) on-chip gelation of the precursor droplets. At 37 °C, the method enabled a ∼35-fold variation of the shear elastic modulus of the agarose gels. The application of the method was demonstrated by encapsulating two mouse embryonic stem cell lines within the agarose microgels. This work establishes a foundation for the high-throughput generation of combinatorial microenvironments with different mechanical properties for cell studies. [Copyright &y& Elsevier]

This article reviews recent developments in the microfluidic preparation of different types of particles made of polymeric and inorganic materials. We discuss control of the particle sizes, morphologies, shapes, and structures in terms of various features of microfluidic synthesis. [ABSTRACT FROM AUTHOR]

Self-organization of nanoparticles is an efficient strategy for producing nanostructures with complex, hierarchical architectures. The past decade has witnessed great progress in nanoparticle self-assembly, yet the quantitative prediction of the architecture of nanoparticle ensembles and of the kinetics of their formation remains a challenge. We report on the marked similarity between the self-assembly of metal nanoparticles and reaction-controlled step-growth polymerization. The nanoparticles act as multifunctional monomer units, which form reversible, noncovalent bonds at specific bond angles and organize themselves into a colloidal polymer. We show that the kinetics and statistics of step-growth polymerization enable a quantitative prediction of the architecture of linear, branched, and cyclic self-assembled nanostructures; their aggregation numbers and size distribution; and the formation of structural isomers. [ABSTRACT FROM AUTHOR]

Abstract: Since the inception of soft lithography, microfluidic devices for cardiovascular research have been fabricated easily and cost-effectively using the soft lithography method. The drawback of this method was the fabrication of microchannels with rectangular cross-sections, which did not replicate the circular cross-sections of blood vessels. This article presents a novel, straightforward approach for the fabrication of microchannels with circular cross-sections in poly(dimethylsiloxane) (PDMS), using soft lithography. The method exploits the polymerization of the liquid silicone oligomer around a gas stream when both of them are coaxially introduced in the microchannel with a rectangular cross-section. We demonstrate (i) the ability to control the diameter of circular cross-sections of microchannels from ca. 40–100 μm; (ii) the fabrication of microchannels with constrictions, and (iii) the capability to grow endothelial cells on the inner surface of the microchannels. [Copyright &y& Elsevier]

We studied the optical properties of hybrid multilayer microspheres (HMMs). We prepared multilayer particles with alternating radial layers of gold nanoparticles (NPs) and poly(methyl methacrylate) and achieved control over particle size, the thickness of particle layers, and the surface coverage of gold NPs. We showed the ability to tune the spectral characteristics of the HMMs, which was based on frequency dispersion of the dielectric constant of polymer–metal NP structures. Good agreement between experimental and theoretical extinction properties of the HMMs was obtained. In comparison with multilayer structures synthesized solely from polymers, hybrid multilayer microspheres have a larger refractive layer contrast between adjacent layers, which is important for practical applications in optoelectronic devices. [ABSTRACT FROM AUTHOR]

Abstract: We present a straightforward, accessible method to covalently pattern proteins in poly(dimethyl siloxane) (PDMS) microchannels. Our approach includes (i) region-specific photografting of a layer of poly(acrylamide) (PAAm) and (ii) bioconjugation of PAAm with a desired protein. The method produces symmetric protein patterns on all channel walls, which have high specificity and pattern fidelity, are compatible with a variety of geometries and exhibit excellent longevity under shear stresses of up to 1dyn/cm. We demonstrate the generality of the method by creating multi-protein gradients within microfluidic microchannels and by in-situ patterning of islands of multiple proteins. Protein activity was observed by the digestion of BODIPY–casein using channels patterned with trypsin. [Copyright &y& Elsevier]

We report the solution-phase formation of ordered lamellar nanocrystal (NC) arrays. These semiconductor lamellae exhibit structural integrity and temporal stability, without recourse to chemical cross-linking. They are many micrometers in diameter yet only two or three nanocrystal layers in thickness. We show that these structures can integrate a cargo of water-soluble ions, molecules, metal nanoparticles, or biomolecules. Encapsulation of gold nanoparticles is found to cause photoluminescence enhancement of the host CdSe nanocrystals. These easily prepared nanocrystal "envelopes" promise properties modulated through the integration of a vast array of water-soluble species. Our approach marks a step toward ordered, compartmentalized, NC-based complexes with controlled architectures. [ABSTRACT FROM AUTHOR]

In vivo, stem cell fate is regulated by local microenvironmental parameters. Governing parameters in this stem cell niche include soluble factors, extra-cellular matrix, and cell-cell interactions. The complexity of this in vivo niche limits analyses into how individual niche parameters regulate stem cell fate. Herein we use mouse embryonic stem cells (mESC) and microcontact printing (μCP) to investigate how niche size controls endogenous signaling thresholds. mCP is used to restrict colony diameter, separation, and degree of clustering. We show, for the first time, spatial control over the activation of the Janus kinase/signal transducer and activator of transcription pathway (Jak-Stat). The functional consequences of this niche-sizedependent signaling control are confirmed by demonstrating that direct and indirect transcriptional targets of Stat3, including members of the Jak-Stat pathway and pluripotency-associated genes, are regulated by colony size. Modeling results and empirical observations demonstrate that colonies less than 100 μm in diameter are too small to maximize endogenous Stat3 activation and that colonies separated by more than 400 μm can be considered independent from each other. These results define parameter boundaries for the use of ESCs in screening studies, demonstrate the importance of context in stem cell responsiveness to exogenous cues, and suggest that niche size is an important parameter in stem cell fate control. [ABSTRACT FROM AUTHOR]

We report the application of the "internal trigger" approach to multistep microfluidic polymerization reactions conducted in droplets, namely, polyaddition and polycondensation. We hypothesized and experimentally established that heat generated in an exothermic free radical polymerization of an acrylate monomer (Reaction 1) triggers the polycondensation of the urethane oligomer (Reaction 2). Completion of two microfluidic polymerization reactions led to the continuous synthesis of polymer particles with an interpenetrating polymer network (IPN) structure. Use of this microfluidic synthesis allowed us (i) to conduct efficient screening of the compositions of the monomer mixtures; (ii) to achieve control of the stoichiometric ratios of reactants in Reaction 2 by varying the flow rates of liquids; (iii) to reach control over the morphology of the resulting particles; and (iv) to produce polymer particles with a narrow size distribution and a predetermined size. [ABSTRACT FROM AUTHOR]

We report a predefined self-organization of gold nanorods (NRs) end-terminated with multiple polymer arms ("pom-poms") in higher-order structures. The assembly of polymer-tethered NRs was controlled by changing the structure of the polymer pom-poms. We show that the variation in the molecular weight of the polymer molecules and their relative location with respect to the long side of the NRs resulted in two competing association modes of the nanorods, that is, their side-by-side and end-to-end assembly, and produced bundles, chains, rings, and bundled chains of the NRs. The superposition of the two variables controlling the organization of NRs allowed us to create a map showing the variation in the longitudinal plasmonic bands of the NAs achieved by their self-assembly. [ABSTRACT FROM AUTHOR]

Complexity in the spatial organization of human embryonic stem cell (hESC) cultures creates heterogeneous microenvironments (niches) that influence hESC fate. This study demonstrates that the rate and trajectory of hESC differentiation can be controlled by engineering hESC niche properties. Niche size and composition regulate the balance between differentiation-inducing and -inhibiting factors. Mechanistically, a niche size-dependent spatial gradient of Smad1 signaling is generated as a result of antagonistic interactions between hESCs and hESC-derived extra-embryonic endoderm (ExE). These interactions are mediated by the localized secretion of bone morphogenetic protein-2 (BMP2) by ExE and its antagonist, growth differentiation factor-3 (GDF3) by hESCs. Micropatterning of hESCs treated with small interfering (si) RNA against GDF3, BMP2 and Smad1, as well treatments with a Rho-associated kinase (ROCK) inhibitor demonstrate that independent control of Smad1 activation can rescue the colony size-dependent differentiation of hESCs. Our results illustrate, for the first time, a role for Smad1 in the integration of spatial information and in the niche-size-dependent control of hESC self-renewal and differentiation. [ABSTRACT FROM AUTHOR]

We report a microfluidic approach to generating capsules of biopolymer hydrogels. Droplets of an aqueous solution of a biopolymer were emulsified in an organic phase comprising a cross-linking agent. Polymer gelation was achieved in situ (on a microfluidic chip) by diffusion-controlled ionic cross-linking of the biopolymer, following the transfer of the cross-linking agent from the continuous phase to the droplets. Gelation was quenched by collecting particles in a large pool of cross-linking agent-free liquid. The structure of microgels (from capsules to gradient microgels to particles with a uniform structure) was controlled by varying the time of residence of droplets on the microfluidic chip and the concentration of the cross-linking agent in the continuous phase. We demonstrated the encapsulation of a controlled number of polystyrene beads in the microgel capsules. The described approach was applied to the preparation of capsules of several polysaccharides such as alginate, κ-carrageenan, and carboxymethylcellulose. [ABSTRACT FROM AUTHOR]

We report a novel approach to continuous and scalable production of core-shell droplets and polymer capsules in microfluidic devices. The described method is also useful in the synthesis of polymer particles with nonspherical shapes. We used capillary instability-driven break-up of a liquid jet formed by two immiscible fluids. Precise control of emulsification of each liquid allowed for the production of highly monodisperse core-shell droplets with a predetermined diameter of cores and thickness of shells. We also achieved control over the number of cores per droplet and the location of cores in the droplet. We carried out fast throughput photopolymerization of the monomeric shells and obtained polymer particles with various shapes and morphologies, including spheres, truncated spheres and, hemispheres, and single and multicore capsules. [ABSTRACT FROM AUTHOR]

Thin liquid layers of polymer solutions, oligomers and monomers, and oligomer–monomer bilayers were used as model systems to explore the mechanism of formation of surface textures in solid coatings and films. It was shown that under particular conditions vertical temperature gradients imposed on these fluid layers induce in them various types of convection. We demonstrated that hexagonal patterns with a high degree of order and symmetry are generated in fluid films undergoing surface tension-driven convection. Various non-equilibrium textures have been trapped in the solid state either by vitrification induced by solvent evaporation from the fluid layer, or by carefully performed polymerization of monomers and oligomers. Finally, we demonstrated that convection patterns can be replicated in convection-passive fluids by bringing them in contact with a fluid layer undergoing convection. [Copyright &y& Elsevier]